Resin composition suitable for use in hair dressing preparations

ABSTRACT

A resin composition useful in hair dressing preparations which comprises the resin-containing liquid obtained by refluxing the following copolymerizable monomeric ingredients under copolymerizing conditions in a water-soluble organic solvent; (1) 5-89 percent by weight of a diacetone acrylamide, (2) 5-40 percent by weight of at least one ester of an alkanol having 4-18 carbon atoms and an acid selected from a group consisting of acrylic acid and methacrylic acid, (3) 6-35 percent by weight of at least one acid selected from a group consisting of acrylic acid, methacrylic acid and itaconic acid, (4) 0-84 percent by weight of at least one ester of an alkanol having one to three carbon atoms and an acid selected from a group consisting of acrylic acid and methacrylic acid.

United States Patent 1191 Kubota et a1.

[451 Jan. 14, 1975 1 1 RESIN COMPOSITION SUITABLE FOR USE IN HAIR DRESSING PREPARATIONS [75] Inventors: Ikuo Kubota, Kawasaki; Masakatsu Mikami, Nara; Isao Konaka, Uzi; Toshihiko Misaki, Kyoto, all of Japan' [73] Assignee: Shinonaga Kasei Co., Ltd., Osaka,

Japan [22] Filed: Feb. 6, 1973 21 Appl. No.: 330,130

Primary ExaminerSam Rosen Attorney, Agent, or Firm-Ladas, Parry, Von Gehr, Goldsmith & Deschamps [57] ABSTRACT A resin composition useful in hair dressing preparations which comprises the resin-containing liquid obtained by refluxing the following copolymerizahlc monomeric ingredients under copolymerizing conditions in a water-soluble organic solvent; 1) 5-89 percent by weight of a diacetone acrylamidc, (2) 54() percent by weight of at least one ester of an alkanol having 41 8 carbon atoms and an acid selected from a group consisting of acrylic acid and methacrylic acid, (3) 6-35 percent by weight of at least one acid selected from a group consisting of acrylic acid, methacrylic acid and itaconic acid, (4) O84 percent by weight of at least one ester of an alkanol having one to three carbon atoms and an acid selected from a group consisting of acrylic acid and methacrylic acid.

12 Claims, N0 Drawings RESIN COMPOSITION SUITABLE FOR USE IN HAIR DRESSING PREPARATIONS BACKGROUND OF THE INVENTION The present invention relates to a resin composition which adheres to hair, exhibiting an excellent hair dressing effect even in hot and highly humid environments.

Recent research in hair dressing materials has been directed to development of a resinous material having the following abilities:

I. To retain the initial shape of the locks curled or set over a prolonged period in any environment;

2. To retain curl and/or wave as set even if the hair is combed or brushed without flaking, that is, without the hair dressing preparation scaling off from the hair like dandruff;

3. To give to the locks a natural appearance and a feel free from stiffness; and

4. To be easily removable from hair by rinsing with warm water or shampooing.

In the conventional hair dressing preparations, shellac, polyvinylpyrrolidone, polyvinyl methyl ether and the like are used as the binding resin. However, these resins have some defects.

Shellac and the related resins are undesirable because they flake, that is, the film formed with these resins is so brittle that it is easily crumbled by combing or brushing, and scales off the hair and deposits like dandruff on the surface of the hair.

Polyvinylpyrrolidone resins are unsatisfactory, too, in that they form a film on hair that is very hard when dried, but readily softens in the presence of moisture, and the difference between the two states is too remarkable. Therefore, the films of these resins easily flake off in the dried state, and easily lose binding power to maintain curls or wave set when the humidity is high.

Use of the polyvinylpyrrolidone resins in which vinyl acetate is copolymerized has been proposed. These copolymers, however, are not quite free from flaking, and the film formed therewith is poor in transparency and therefore give locks an unnatural appearance.

Polyvinyl methyl ether is extremely sticky and therefore this resin can be used only as a plasticizing additive to polyvinyl pyrrolidone.

Resins known to be free from the above-mentioned defects include copolymers of vinyl methyl ether and maleic anhydride; copolymers of vinyl acetate and an ester of crotonic acid, acrylic acid or methacrylic acid; copolymers of vinylpyrrolidone and an acrylic acid ester etc., and by neutralizing the carboxylic groups contained in said copolymers resins giving watersoluble films are provided.

However, these resins do not exhibit satisfactory curl retention. Hair that is curled and/or set by means of a preparation containing one or more of these resins generally retains the curl or set no longer than several hours, and, in a hot and humid environment, that is, in a bathroom or in rainy weather, for instance, retention power is quickly lost.

Accordingly there has been demand for a further improved binding resin for use in hair dressing preparations.

SUMMARY OF THE INVENTION The present invention relates to a novel resin composition which has strong adhesive power, and excellent curl retention even in a hot and highly humid environment and is free from flaking.

This invention is based on the discovery that the foregoing desirable properties useful in hair dressing preparations can be achieved by employing a liquid resin composition which comprises a resin-containing liquid obtained by refluxing the following polymerizable monomeric ingredients under copolymerizing conditions in a water-soluble organic solvent: (1) 5 89 percent by weight of diacetone acrylamide, (2) 5 40 percent by weight of at least an ester of an alkanol having four to 18 carbon atoms and an acid selected from a group consisting of acrylic acid and methacrylic acid, (3) 6 35 percent by weight of at least one acid selected from a group consisting of acrylic acid, methacrylic acid and itaconic acid, and (4) 0 84 percent by weight of at least one ester of an alkanol having one to three carbon atoms and an acid selected from a group consisting of acrylic acid and methacrylic acid.

More preferably, the resin composition of this invention comprises a resin-containing liquid obtained by polymerization of a copolymerizable monomeric mixture consisting of( 1) 10 percent by weight of diacetone acrylamide, (2) l0 30 percent by weight of an ester of an alkanol having four to 18 carbon atoms and an acid selected from a group consisting of acrylic acid and methacrylic acid, (3) l0 20 percent by weight of at least one acid selected from a group consisting of acrylic acid, methacrylic acid and itaconic acid, and (4) 20 70 percent by weight of an ester of alkanol having one to three carbon atoms and an acid selected from a group consisting of acrylic acid and methacrylic acid.

Further more preferably, the resin composition of this invention comprises a resin containing liquid obtained by polymerization of a copolymerizable monomeric mixture consisting of (l) 20 30 percent by weight of diacetone acrylamide, (2) l5 30 percent by weight of an ester of an alkanol having four to 18 carbon atoms and an acid selected from a group consisting of acrylic acid and methacrylic acid, (3) l0 20 percent by weight of at least one acid selected from a group consisting of acrylic acid, methacrylic acid and itaconic acid, and (4) 30 percent by weight of an ester of alkanol having one to three carbon atoms and an acid selected from a group consisting of acrylic acid and methacrylic acid.

The resin composition of this invention is especially suitable for use in hair dressing preparations in the form of pressurized packaging or aerosols. The neutralized composition of this invention is soluble in water and most of the water-miscible organic solvents and its solution in such a solvent exhibits a good mutual solubility with the usual pressurized packaging propellents. The neutralized copolymer, that is, the main binder component, contained in the composition of this invention, can be easily removed from hair by washing with warm water or a usual shampoo.

Now the invention is explained in detail with respect to the constituents of the copolymer constituting the main component of the composition of this invention and the reason for the numerical restrictions imposed on the proportions of the constituents.

Diacetone acrylamide, which is referred to as monomer constituent (l is water-soluble and its homopolymer is a hygroscopic but water-insoluble substance. Diacetone acrylamide has the formula N-( 1,1-dimethyl-3- oxobutyl)acrylamide. It is produced by The Lubrizol Corporation, (Cleveland, Ohio). When this constituent makes up less than percent by weight in the copolymer, the resulting copolymer is, as the whole, insufficiently hydrophilic and is poor in affinity to hair, and therefore the hair dressing preparation comprising this copolymer composition is less spreadable in hair. The copolymer containing more than 89 percent by weight of this monomer constituent is improper in that the resulting film is so hard and brittle. Such a large content of this monomer is improper, too, in consideration of the contents of the other necessary constituents, that is, monomer constituent (3) which contributes to improvement in flexibility and washing-out property of the resulting film and monomer constituent (2) which contributes to hardness of the resulting film and compatibility with the propellent gas.

The monomer constituent (2) must constitute at least 5 percent by weight. Otherwise, a pressurized product (aerosol) system containing such a resin composition is unstable in the coexistence with a halogenated hydrocarbon or liquefied petroleum gas propellent. Further, the resulting film has poor flexibility and flakes. On the other hand when the copolymer contains more than 40 percent by weight of this monomer constituent, the copolymer is only slightly soluble in water and is not easily removed by shampooing. Also such a copolymer gives extremely sticky film which collects dust and soils the hair.

The content of monomer constituent (3), that is, acrylic acid, methacrylic acid, itaconic acid or a mixture thereof, is varied in accordance with the contents of the monomers of classes (1), (2) and (4) so as to provide stable pressurized product systems. When the copolymer contains monomer constituent (3) in an amount of less than 6 percent by weight, the resulting film is water-insoluble. Whereas, the copolymer containing more than 35 percent by weight of this comonomer gives film which is excessively hygroscopic and sticky.

The monomer constituent belonging to class (4) is an ester of an alkanol having one to three carbon atoms and acrylic acid or methacrylic acid. This monomer constituent helps to render the film formed of the resulting resin composition flexible and adhesive. This monomer constituent is not an indispensable component in this invention.

In order to obtain the resin composition with which the object of this invention is achieved, the monomer constituents (l) and (3), which contribute to the enhancement of the hydrophilic property of the copolymer, and the monomer constituents (2) and (4), which contribute to the increment in the hydrophobic property thereof, must be combined in a proper proportion. Namely, if the monomer (1 alone is combined with the monomer (2) and (4) or (2) alone, the resulting resin composition lacks water-solubility and thus it is not easily removed from hair by washing. Whereas, when monomer (3) alone is combined with monomer (2) and (4) or (2) alone, if the content of the monomer (3), which is the hydrophilic constituent, is low, the resulting resin composition is difficult to wash out; and if the content of the monomer (3) is high, the resin composition becomes too sticky because of its hygroscopic property, and cannot hold curls or wave set for long.

Therefore, it is necessary to combine all of the monomer constituents (l), (2), (3) and (4) in a proper proportion so that the films formed on hair by spraying a hair dressing preparation containing the resulting resin composition may have the desirable combination of water-solubility, hardness and adhesion to hair, which properties are not degraded even at elevated temperatures and/or under high humidity.

For the solution polymerization of said monomers, usually a water-soluble aliphatic alcohol having one to four carbon atoms or a mixture of such alcohols is used as the solvent or reaction medium. A water-containing alcohol, such as percent ethyl alcohol, can be used as the solvent. The polymerization is carried out with stirring at the boiling temperature of the used solvent or at a temperature proximate thereto.

It is an additional advantage of this invention that the control of temperature during polymerization can easily be accomplished and homogeneous polymer products are obtained.

In this invention the polymerization can be practiced in the well known manner in which a polymerization catalyst, e.g., peroxides such as benzoyl peroxide, acetyl peroxide, lauroyl peroxide, etc. and azo-compounds such as azo-bis-isobutyronitrile is suitably employed.

The resin-containing composition resulting from the solution polymerization of the mixture of said monomers is usually neutralized by the addition of a watersoluble basic substance so as to produce the watersoluble resin composition of this invention. Examples of such basic substances are ammonia water, lithium hydroxide, sodium hydroxide, potassium hydroxide, mono-, di-, or tripropanolamine, ammonium salts of lysine or glycine, amino methyl propanol, amino methyl propanediol, and the mixtures thereof, etc.

Since an organic amine compound gives a water-free composition, such an amine compound is preferably used when the resin composition is intended to be used in pressurized package (aerosols) systems where existence of water is generally deleterious.

In another embodiment of this invention the resin composition may additionally contain various additives, such as glycerine, ethylene glycol, sorbitol, polyethylene glycol, lanoline, or dimethyl phthalate for modifying the hardness of the resulting film.

The liquid resin composition for hair dressing preparations obtained by the present invention can be packed in a sealed vessel with or without being dissolved in an water soluble organic solvent, such as an alkanol having one to four carbon atoms, dioxane, methyl ethyl ketone, acetone, ethyleneglycol monomethyl ether, ethyleneglycol monoethyl ether, etc., pressurized with a propellent as pressurized package products. The propellents to be used in such a case includes halogenated hydrocarbons mainly composed of dichlorodifluoroethane, trichloromonofluoromethane, and/or dichlorotetrafluoroethane; liquefied petroleum gases mainly composed of propane and butane; dimethyl ether, carbon dioxide, or' mixtures thereof, which are conventionally used.

Excellent pressurized (aerosol) hair dressing preparations (hair lacquers) can be provided by employing the resin composition of the present invention. That is, the composition is dissolved in an water-soluble organic solvent in a proportion that its solid content is 0.5

- percent by weight of the mixture, and then 25 75 percent by weight of the thus formed mixture and 75 25 percent by weight of any of the abovementioned propellents are packed in a sealed vessel.

Further, the resin composition of this invention, which is soluble in water and an water-soluble organic solvent can be used as an ingredient for nonpressurized hair dressing and other cosmetic preparations, such as hair cream, hair lotion, or shaving cream, with addition of the other hair dressing materials. It is also possible to use the resin composition of the invention atomizing by means of an ejector unit such as disclosed in British Pat. Nos. 1,148,484 and 1,172,274.

In still another embodiment of this invention, the resin composition can be used as a film-forming ingredient for beauty packs and as a coating preparation for protecting wounds in the skin.

The invention is best illustrated by the following examples, which are given merely for the exemplary purpose. It is not intended that these examples limit the scope of the invention or the manner in which the present invention can be practiced.

DESCRIPTION OF PREFERRED EMBODIMENTS:

Example 1 Into a four-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer and an agitator, 250 g of methyl acrylate, 300 g of methyl methacrylate, 150 g of lauryl (dodecyl) methacrylate, 200 g of diacetone acrylamide, 40 g of acrylic acid, 50 g of methacrylic acid, 10 g of itaconic acid, and 500 g of ethyl alcohol were placed and 3 g of benzoyl peroxide was added thereto. The mixture was refluxed for polymerization by heating at 80 82C on a hot bath with constant agitation. After 3 hours further 3 g of benzoyl peroxide disperesed in 50 g of ethyl alcohol was added and heating was continued. After 1.5 hours, a solution of the copolymer in ethyl alcohol was obtained whereby the conversion was 98.5 percent. Then, a solution of 96.3 g of aminomethyl propanediol and 200 g of ethyl alcohol were added to the solution of the copolymer through the dropping funnel and additonally 350 g of ethyl alcohol was supplied, whereby a resin composition containing 50 percent of the nonvolatiles was obtained. The viscosity of this product composition at 20C was about 27,000 centipoises. The conversion was calculated by measuring the amount of the nonvolatile materials therein and the viscosity was measured by a Brookfield type viscometer.

Ten grams (10g) of the thus obtained composition was dissolved in 90 g of ethyl alcohol, and then a perfume was added to the mixture. This mixture was placed in an aerosol container and packed with 150 g of a mixture of equal amounts of trichloromonofluoromethane and dichlorodifluoromethane (1:1 by weight) according to the conventional pressurized packaging technique so as to make a hair lacquer product.

Example 2 Into the same four-necked flask as used in Example 1, 140 g of ethyl acrylate, 150 g of ethyl methacrylate, 300 g of stearyl (octadecyl) acrylate, 250 g of diacetone acrylamide, 65 g of acrylic acid, 75 g of methacrylic acid, 20 g of itaconic acid, 200 g of ethyl alcohol, and 300 g of isopropyl alcohol were placed and 3.5 g of azo-bis-isobutyronitrile was added thereto. The

mixture was refluxed for polymerization by heating at 88 90C for 3.5 hours. Thereafter further 1.5 g of azo-bis-isobutyronitrile dispersed in 50 g of ethyl alco hol was added and heating was continued. After 1 hour, a solution of a copolymer in ethyl alcohol was obtained at a conversion of 99 percent. Then a solution of 278.86 g of triisopropanolamine in 300 g of isopropyl alcohol was added to the solution of the copolymer and additionally 420 g of ethyl alcohol was supplied whereby a resin composition containing 50 percent of nonvolatile materials was obtained. The viscosity of this product composition at 20C was about 15,000 centipoises.

Ten grams (10g) of the thus obtained composition a was diluted with 90 g of ethyl alcohol, and then a perfume was added to the mixture. This mixture was placed in an aerosol container and was packed with 150 g of a liquefied gas comprising trichloromonofluoromethane and dichlorodifluoromethane (1:1 by weight) according to the conventional pressurized packaging technique.

Example 3 The following copolymerization was carried out in accordance with the procedure of Example 1. Three hundred and fifty grams (350g) of methyl acrylate, 50 g of butyl acrylate, 25 g of butyl methacrylate, 175 g of stearyl (octadecyl) methacrylate, 250 g of diacetone acrylamide, 65 g of acrylic acid, g of methacrylic acid, and 20 g of itaconic acid were mixed with 500 g of ethyl alcohol. To this mixture, 12 g of benzoyl peroxide was added and the whole mixture was heated at 78 80C for polymerization. After 3 hours, further 2 g of benzoyl peroxide dissolved in 20 g of ethyl alcohol was added twice with an interval of 30 minutes. Thus a copolymer was formed at the conversion of 99.5 percent. The thus obtained resin-containing liquid was neutralized by adding 167.67 g of aminomethyl propanol dissolved in 200 g of ethyl alcohol. The neutralized liquid was further diluted by adding 407 g of ethyl alcohol so that the non-volatile content thereof become about 50 percent by weight.

The viscosity of the thus obtained resin composition was 32,000 cps (measured by a Brookfield viscometer).

Ten grams (10g) of the thus obtained composition was dissolved in g of ethyl alcohol, and a perfume was added to the mixture. This mixture was placed in an aerosol container and packed with g of a mixture of trichloromonofluoromethane and dichlorodifluoromethane (1:1 by weight) according to the conventional pressurized packaging technique so as to make a hair lacquer product.

Also a set lotion was prepared by dissolving 20 g of the thus obtained resin composition (solution) in 56 g of ethyl alcohol and 24 g of water and adding 0.2 g of a perfume. This set lotion was placed in an spray bottle with a manually operated spray pump and used for evaluation. This set lotion exhibited a good curl retention without flaking.

Examples 4 10 In the same way as in Example 1 3, copolymers were prepared, the proportions of the monomer constituents of which are shown in the following Table 1.

Aerosol hair lacquers were prepared using each of the obtained resin compositions in the same way as in Examples 1 3.

The performance of the hair lacquers prepared in all cellent. Curl retention of 65 percent or more was rated as good. Curl retention of 50 percent or more was rated as allowable." Curl retention less than 50 percent was rated as poor.

these examples was examined by the curl retention test, 5 The solubility or the wash-out property of the resin which evaluates moisture resistance of the formed composition was evaluated by measuring the time remembrane, the solubility test, which evaluates washquired for a membrane 10 mm X 10 mm in area and 0.1 out property of the membrane, the test for compatibilmm in thickness formed with the prepared resin com ity with aerosol propellents and the Sword Rocker position to dissolve in water at 20C. Dissolution time hardness test andthe flaking resistance test. 10 60 seconds or less was rated as excellent." Ninety sec- The curl retention was calculated in accordance with e ds or less was rated as good, 120 seconds or less the following equation: as allowable and more than 120 seconds as poor. Curl retention (percent) (L L,)/(L L,,) X 100 The compatibility in the aerosol formulation was dewhereby termined by measuring the amount of dichlorodi- L: length of a straight specimen (a bundle of hair). fluoromethane that can be homogeneously mixed with L length of a curled specimen prior to the test. 10g of an ethanol solution containing 5 percent by L,: length of a curled specimen after subjected to weight of the prepared copolymer at C. Twentyfive humid condition for a predetermined period of grams or more was rated as excellent, 20 g or more time. as good, 15 g or more as allowable and less than I u In The test conditions were as follows: For the resin comg fth f d br Y t d b positions of Examples 1 to 3, the temperature range 8 3 g f a z l g 2 was 38 40C and RH was 95 percent. For the resin means 0 e Wm 06 er ar 8 r Rocker value 50 or more was rated as excellent. 40 compositions of all the other examples, the tempera- H t,

0 or more was rated as good, 30 or more as allow ture was 30 C and RH was 90 percent, and test samples u able and less than as poor. were kept for 10 hours under the humid condition.

- The flaking resistance was evaluated by combing and Greater curl retention values (percent) represent betbrushing a bundle of hair on which the hair lacquer had ter curl retention, that 18, better moisture resistance, H and 1007 curl retention means erfect retention been Sprayed and dried and subjectively rated as ex- 0 p cellent, good, allowable" and poor. Curl retention of 80 percent or more after 10 hours 30 The results of the evaluation tests are summarized in under the humidity 90 95 percent was rated as ex- Table 1.

Table l Ex. l lonomer(l) Monomer(2) Monomer(3) Monomerui) Curl Wash-out Compatibility Hardness 1' laltlllg retention property in aerosol 01 coal lug formulation memberauu AA 4 MA l- UAA 2O LMA l5 MAA 5 lo 25 55 ex ell nt excellent good excellent excel l out 1A 1 MMA30 AA e. 5 EA 4 2. DAA 25 SA 30 MAA 7.5 lb 1 29 e cell t good excel Lent good excel I out lA 2 EMAlS AA o. 5 MA 3- UAA 5 SMA 7- 5 MAA 7. 5 16 BA 5 12.5 good excellent good excell ent excel 1 out 1A 2 anA 2.5

AA 3 EA 2U UAA l0 EHM-A 30 MAA 5 l0 EMABU excellent allowable excellent ,tg'ood ,euorl 1A 2 AA 5 MA 5- UAA 10 5A 1.0 MAA 3. 5 l0 0 v 35 good allowable allowable good oxcoll out 1A 3 LNA 3 5 7 AA :5 o. DAA ()0 SA l0 MAA 20 EA l0 allowable excellent allowable allowable allowable AA 3 T. UAA ()0 SA 30 MAA 5 l0 0 good good excellent excellent ull unable AA 5 UAA Ll LMA 20 i- 20 EA 5 5 D09! excellent good allowable cxco l 1 exit AA 5 9- UAA 20 LMA 2U TAAM; 20 EA 40 S good excellent excellent excel 1 out AA 2 BAA LMA 4 1112A 3 b 0 good good stood excellent hoor AA 5 ll. UAA 20 LMA 4 MAAlU 20 BA 50 56 excellent x ellent; oor oor oxen l I out AA 5 1.2.. UAA 2t) LMA ll MAALU 20 EA 19 i9 excellent poor excoll out excel! t-ut ,t' o l alkanol having one to three carbon atoms and an acid selected from a group consisting of acrylic acid and methacrylic acid.

2. A resin composition as set forth in claim 1,

wherein the copolymerizable monomeric mixture esamp; n t .1l Ex. Monomer-(1) Monomer-(2) Monomer-(3) blonomerut) Curl Compatibility Hardnelfl fl;

(96) (94) (96) (96) r t ti property in aerosol of coating AA 2 formulation memberane DAA 2U LMA 2U MAA 2 5 EA 55 55 exCel-ient poor excellent good excellent AA 11 14. UAA 2U LMA 20 MAAZO 1U. EA l9 19 poor excellent poor r um] In Table 1 10 sentially consists of (l) 10 60 percent by weight of di- 3}; e acetone acrylamide, (2) 10 30 percent by weight of SA Stearyl acrylate at least one ester of an alkanol having four to 18 carbon SMA Stearylmethacrylate EHMA Ethyl hexyl methacrylate atoms and an acid selected from a group consisting of AA Acrylic acid acrylic acid and methacrylic acid, (3) 10 20 percent IMAA :vietlia r ii daeid by weight of at least one acid selected from a group 3 z ggi ig consisting of acrylic acid, methacrylic acid and itaconic MMA Methyl methacrylate acid, and 4 70 percent by weight of at least one EA Ethyl acrylate 1 EMA Ethyl methacrylate ester of an alkanol having one to three carbon atoms BA Bum acrylm and an acid selected from a group consisting of acrylic BMA Butyl melhacrylale acid and methacrylic acid.

20 The results of the curl retention test carried out with fesln composltlon as set ford} respect to the hair lacquers prepared with the resin whelem the f p y monomerlc mixture composition of Examples 1 3 are summarized in selltlally conslstsPf 1 20 30 Percent y Weigh? Ofdl- Table 2 in comparison with the results of the same test acetone acrylamlde, k 30 Percent y Weight of with respect to several hair lacquer products on the an ester of an alkalloi haymg four to 13 carbon atoms market and at least one acid selected from a group consisting Table 2 Time (hr.) Sample 0.5 1.0 1.5 2.0 2.5 3.0 10.0

Sam' A 92.0% 88.5% 81.5% 78.0% 75.5% 72.0% 42.0% ples on B 95.0% 93.0% 88.0% 85.0% 81.5% 77.0% 58.0% the C 91.0% 88.0% 78.0% 71.5% 63.0% 56.0 15.0% market D 97.0% 92.5% 90.5% 88.5% 84.0% 73.0% 200% Sample from example 1 97.0% 96.0% 93.0% 91.5% 89.0% 85.5% 70.0% Sample from example 2 96.0% 91.0% 88.0% 82.5% 78.0% 77.0% 660% Sample from example 3 98.0% 94.5% 92.5% 90.0% 87.5% 83.0% 67.5%

Using these resin compositions, non-pressurized hair of acrylic acid and methacrylic acid, (3) l0 20 perdressing preparations such as hair lotions and hair cent by weight of at least one acid selected from a creams as well as skin cosmetics such as beauty packs group consisting of acrylic acid, methacrylic acid and and protective skin coatings were prepared. There was itaconic acid, and (4) 63 percent by weight of at no difficulty in the preparation thereof as in preparaleast one ester of an alkanol having one to three carbon tion of the pressurized products. atoms and an acid selected from a group consisting of Development of various products using the resin acrylic acid and methacrylic acid. composition of this invention is under way. 1 4. A resin composition as set forth in claim 1 which is neutralized with a basic substance.

What we claim is.

5. A resin composition as set forth in claim 2 which 1. A resin composition useful in hair dressing prepais neutralized with a basic ubsta e, rations which comprises the resin-containing liquid ob- 6, A resin iti as t f h i l i 3 hi h tained by refluxing the following copolymerizable monis neutralized with a basic substance. omeric ingredients at 78 90 C. in a water-Soluble Or- 7. A resin composition as set forth in claim 4 which ganic solvent: is diluted with an water-miscible solvent.

89 Percent y weight of a dlacetone acrylam' 8. A resin composition as set forth in claim 5, which f is diluted with an water-miscible solvent.

2, 40lprprc entfby weiglhst of it least one eser O 9. A resin composition as set forth in claim 6, which a favmg to g z g gl $5 22 is diluted with an water-miscible solvent. fi ifi i yf z ggg up a y 10. A pressurized packaging system for hair dressing om r' 3. 6 35 percent by weight of at least one acid sef p 18mg the composltlon of Glam 7 and a propel lected from a group consisting of acrylic acid, methacrylic acid and itaconic acid, 11. A pressurized packaging system for hair dressing 4. 0 84 percent by weight of at least one ester of an Comprising the Composition of Glam 8 and a P p lent.

12. A pressurized packaging system for hair dressing comprising the composition of claim 9 and a propellent. 

2. A resin composition as set forth in claim 1, wherein the copolymerizable monomeric mixture essentially consists of (1) 10 - 60 percent by weight of diacetone acrylamide, (2) 10 - 30 percent by weight of at least one ester of an alkanol having four to 18 carbon atoms and an acid selected from a group consisting of acrylic acid and methacrylic acid, (3) 10 - 20 percent by weight of at least one acid selected from a group consisting of acrylic acid, methacrylic acid and itaconic acid, and 4 20 - 70 percent by weight of at least one ester of an alkanol having one to three carbon atoms and an acid selected from a group consisting of acrylic acid and methacrylic acid.
 2. 5 - 40 percent by weight of at least one ester of an alkanol having four to 18 carbon atoms and an acid selected from a group consisting of acrylic acid and methacrylic acid,
 3. 6 - 35 percent by weight of at least one acid selected from a group consisting of acrylic acid, methacrylic acid and itaconic acid,
 3. A resin composition as set forth in claim 2, wherein the copolymerizable monomeric mixture essentially consists of (1) 20 - 30 percent by weight of diacetone acrylamide, (2) 15 - 30 percent by weight of an ester of an alkanol having four to 18 carbon atoms and at least one acid selected from a group consisting of acrylic acid and methacrylic acid, (3) 10 - 20 percent by weight of at least one acid selected from a group consisting of acrylic acid, methacrylic acid and itaconic acid, and (4) 30 - 63 percent by weight of at least one ester of an alkanol having one to three carbon atoms and an acid selected from a group consisting of acrylic acid and methacrylic acid.
 4. A resin composition as set forth in claim 1 which is neutralized with a basic substance.
 4. 0 - 84 percent by weight of at least one ester of an alkanol having one to three carbon atoms and an acid selected from a group consisting of acrylic acid and methacrylic acid.
 5. A resin composition as set forth in claim 2 which is neutralized with a basic substance.
 6. A resin composition as set forth in claim 3 which is neutralized with a basic substance.
 7. A resin composition as set forth in claim 4 which is diluted with an water-miscible solvent.
 8. A resin composition as set forth in claim 5, which is diluted with an water-miscible solvent.
 9. A resin composition as set forth in claim 6, which is diluted with an water-miscible solvent.
 10. A pressurized packaging system for hair dressing comprising the composition of claim 7 and a propellent.
 11. A pressurized packaging system for hair dressing comprising the composition of claim 8 and a propellent.
 12. A pressurized packaging system for hair dressing comprising the composition of claim 9 and a propellent. 